Treatment of hydrocarbon oils and coal



' Jan. 1, 1935. J. (#MORRELL 1,986,593

TREATMENT OF HYDROCARBQN OILS AND GOAL Filed May 14, 1931 INVENTOR IJAcQUE Q. MORRELL BY Z MQ ATTORN 10 under tities of relatively PatentedJan. 1 1935 Jacque C. 'Morrell, Chicago, 111., assignor to Universal OilProducts Company, Chicago, 111., a corporation of South DakotaApplication May 14, 1931, Serial No. 537,233

6 Claims.

This invention relates to the treatment of hydrocarbon'oils and coal andparticularly refers to the simultaneous conversion of relatively heavyoils and coal into lighter and more valuable liquid products andcarbonaceous residue.

It has been proposed, as an economic process in localities where coal isplentiful, to convert mixtures or a suspension of pulverized or powderedcoal in a relatively heavy hydrocarbon oil, elevated temperatures andsubstantial superatmospheric pressures, into lighter and more valuablehydrocarbon liquid products, such as, for example, motor fuel. andsubstantially dry carbonaceous residue. Difliculties have beenencountered in suchprocesses under someconditions of operation bycarbonization of the 'heatmg element through which the coal andoilfnixture is passed when conversion temperatures sufliciently high toeffect the production of maximum quanlight desirable products such asmotor fuel are employed. The present invention overcomes this difficultyby providing a secondary charging stock which preferably comprises ahydrocarbon oil which is not so easily coked or carbonizedas the coaland oil mixture, said secondary charging stock being subjected to higherconversion temperatures than those to which the coal and mixture of oilis subjected. The two streams of heated material are commingled, eitherin the coking zones of the system, or prior to their introductionthereto, the relatively highly heated oil serving as a means ofincreasing the temperature of the coal and oil mixture to the desireddegree, after passage of the latter through the heating element.

A specific embodiment of the present invention may comprise: subjectinga mixture of hydrocarbon oil and pulverized or powdered coal toconversion conditionsin a heating element, introducing the heatedproducts into a reaction zone wherein vaporous and non-vaporousconversion products may be reduced to a substantially dry carbonaceousresidue, subjecting vapors from said reaction zone to fractionation,subjecting. the desirable components of the vapors to condensation andcooling and collecting the resulting products, returning the relativelyheavy insufiiciently converted components of the vapors which may becondensed in the fractionating zone to further conversion in the samecracking system and subjecting a secondary charging stock toindependently controlled conversion conditions in a secondary heatingelement under a higher conversion 1 temperature than that to which thecoal and oil mixture has been subjected, thence commingling the streamof heated secondary charging stock with the heated coal and oil mixtureand introducing the stream of commingled materials into said reactionzone. 5

As a feature of the present invention the insufficiently convertedintermediate products of the process, which may becondensed from thevapors during fractionation thereof, may be returned for furthertreatment either with the coal and oil mixture or with the secondarycharging stock and except in cases where the secondary charging stockisa relatively light distillate such as, for example, a light gas oil,kerosene distillate, naphtha or straight-run motor fuel, saidintermediate products are preferably returned for retreatment, togetherwith said secondary charging stock. When naphtha or gasoline is employedas a secondary. charging stock, it is among the objects of the inventionto reform the same to improve the anti-knock value.

The attached diagrammatic drawing illustrates one form of apparatusembodying the principles v of the present invention. A mixture ofcoaland oil, the coal preferably being finely dispersed and suspended inan oil sufliciently heavyto function as a carrying medium, may besupplied through line 1 and valve 2 to pump 3 from which it may be fedthrough line 4 and valve 5 intoheating element 6 which is located withinany, suitable form 'of furnace 7 capable of supplying the required heatto the material undergoing treatment. The heating element is preferablyof such form that the mixture is passed therethrough at relatively highvelocity and preferably the mixture is maintained in a turbulent stateduring heating to prevent deposition of coal-in the heating element. Thecoal and oil mixture, after being heated to the desired temperature,preferably under a substantial super-atmospheric pressure, may bedischarged through line 8 and valve 9 and may pass either thri ugh line10 and valve 11 into reaction chamber 12 or through line 10' and valve11' into reaction chamber 12' or may be discharged, in part, into bothof these chamberssimultaneously. The temperature and pressure conditionsemployed in heating element6 may be within or somewhat below the rangeof conversion conditions and, preferably the conditions under which theoil and coal mixture is subjected to treatment in this zone aresuflicient to initiate and effect substantial conversion of' said coaland oil mixture but are not sufliciently severe to cause any substantialdeposition of carbouau Ousmaterial prior to the introduction of thestream of heated material into the reaction zone.

Reaction chambers 12 and 12' are similar zones preferably maintainedunder substantial supera other is being used, or, if desired, the twochambers may be operated simultaneously, the purpose in either casebeing to prolong the operating cycle. It-will be understood that whiletwo reaction chambers are illustrated only one chamber or, if desired,more than two chambers may be employed without departing from the spiritof the invention. Drawoff lines 13 and 13' controlled by valves 14and'14' respectively, are provided on chambers 12 and l2" respectively,to permit the removal of water and/or of any liquid residual product,when desired. Vapors may be withdrawn from chamber 12 through line 15and valve 16 while vapors may be withdrawn from chamber 12 through line15 and valve 16. The vapors from the reaction zones may pass throughline 1'7 and valve 18 to fractionation in fractionator 19, which may beof any suitable and well known form capable of separating the relativelylight desirable components of the vapors from their heavierinsufliciently converted components.

The relatively light desirable compone'ntsof the vapors may pass fromiractionator 19 through line 20 and valve 21, may be subjected tocondensation and cooling in condenser 22, uncondensable gas anddistillate from which may pass through line 23 and valve 24 to becollected in receiver 25. Uncondensable gas may be released from thereceiver through line 26 and valve 27.

Distillate may be withdrawn from the receiver through line 28 and valve29. A portion of the distillate may, if desired, be withdrawn fromreceiver 25 through line 26 and valve 27' to pump 28' by means of whichit may be recirculated through line 29' and valve 30 to the upperportion of fractionator 19, wherein it may serve as a cooling andrefluxing medium, assisting fractionation of the vapors and controllingtheir outlet temperature.

The relatively heavy insufliciently converted components of the vapors,which may be condensed in fractionator 19, may pass therefrom throughline 31 and valve 32 to pump 33 by means of which they may be returnedto the cracking system for further conversion, passing through line 34and either through line 35, valve 36 and line 4 into heating element 6or, preferably,

through line 37, valve 38 and line'39 into a separate heating element 47or, ii desired, this oil may be directed, in part, to each of theheating elements 6 and 4'7. That portion, if any, of the re-- fluxcondensate from fractionator 19 which is returned to heating element 6is subjected to retreatment therein together with the coal and oilmixture supplied to the process. That portion, if any, of the refluxcondensate from fractionator 19, which is returned for retreatment toheating element '47, is subjected to conversion conditions in this zone,together with a secondary charging stock, preferably comprising an oilwhich is not easily coked or carbonized under conversion conditionssomewhat more severe than the conditions employed in heating element 6.The secondary charging stock may be supplied through line 40 and valve41 to pump 42, being fed therefrom through line 39 and valve 43 toheating element 47. This secondary charging stock may correspond incharacteristics to the reflux condensate from fractionator 19 or maypossess different characteristics and said reflux condensate may besubjected to retreatment together with the coal and oil mixture,depending upon which said secondary charging stock or together with ofthe conversion conditions, those employed in heating element .6 or thoseemployed in heating element 47, are best suited to effect furtherconversion of said reflux condensate into maximum yields of thedesirable products. For example, if

the reflux condensate and the secondary charging stock are bothrelatively light; low boiling oils possessing similar characteristicswith respect to their ideal conversion conditions they are preferablycommingled and subjected to conversion in heating element 4'1. 0n theother hand if for example, the secondary charging stock is a relativelylight distillate such as naphtha or straight-run gasoline and the refluxcondensate is a heavier oil which might be over-cracked into excessiveyields of gas and coke if subjected to the conversion conditionsdesirable for the secondary charging stock, saidreflux condensate ispreferably returned for retreatment together with the primary chargingstock. It may be desirable to blend a portion of the reflux condensatewith each of the two streams of charging stock in order to somewhatalter the character thereto is preferably subjectedto conversionconditions more severe than the conditions employed in heating element6. A substantial super-atmospheric pressure is preferably employed inheating element 4'7, although substantially atmospheric or relativelylow super-atmospheric. pressures may be employed in this zone,ifdesired. The stream of heated oil may be discharged from heatingelement 47 through line 45 and-valve 46, conmiingling with the stream ofheated coal and oil mixture discharged from heating element 6, servingto increase the temperature of the latter for the purpose of eflectingits further conversion and passing therewith either through line 10 andvalve 11 into reaction chamber 12 or through line 10' and valve 11 intoreaction chamber 12 or partially to both of these zones, whereinconversion of the commingled materials may continue and where,as'already described, the residual conversion products may be reducedto-a substantially dry carbonaceous material. It will be readilyunderstood that the two streams of heated material may be commingledeither within or prior to their introduction into the coking or reactionchamber, although for the sake of simplicity, no alternative is shown inthe drawing.

Pressures employed within the system may range from substantiallyatmospheric to superatmospheric pressures as high as 2000 pounds persquare inch or more. Temperatures employed in F. more or less. The

the heating elements may range from 650 to 1200 heating element in whichthe coal and oil mixture is treated may employ temperatures below theconversion range or.rel-- atively mild conversion temperatures, saidtemperatures ranging preferably from 650 to 900 F. or thereabouts,depending primarily upon the percentage and type of coal and its degreeof dispersion or suspension in the oil, the type of oil which the coalis admixed with, and upon the pressure conditions employed. Preferablysubstantial super-atmospheric pressures of the order of.100 to 500pounds per square inch are employed in the primary heating element.Substantial super-atmospheric pressures of about this same range mayalso be employed in the reaction chambers although the reaction chambersmay; if desired, be operated under reduced pressure relative to thatemployed in theprimary heating element and, if desired, may employsubstantial ly atmospheric or relatively low super-atmosphericpressures. Preferably, substantially higher temperatures of the order of900 to 1200" F. are employed in the heating element in which thesecondary charging stock is treated and pressures ranging fromsubstantially atmospheric to super atmospheric pressures as high as 500pounds per square inch or more may be employed in this zone. In general,relatively low pressures are used with the higher temperatures andvice-versa. If a relatively low pressure is employed in the secondaryheating element substantially the same or lower pressures must, ofcourse, be employed in the reaction chambers. The fractionating,condensing and collecting equipment may be maintained under any desiredpressure ranging from substantially atmospheric to 500 pounds per squareinch or more super-atmospheric.

As a specific example of the operation of the process .of the presentinvention, the primary charging. stock comprises a fuel oil of about 16-A. P. I. gravity with. which has been mixed about 50% by weight of theraw oil, of pulverized bituminous 'coal. The coal and oil mixture issubjected in the primary heating element to a. temperature of about 850F. under a super-atmospheric pressure of about 500 pounds per squareinch. Reflux condensate from the fractionator of the system is returnedtothe primary heating element for further treatment, together with thecoal and oil'mixture- A secondary charging stock comprising astraight-run gasoline of low anti-knock value is subjected in thesecondary heating element to a temperature of about 1000 F., under asuper-atmospheric pressure of about 400 pounds per square inch. Thestream of heated oil from the secondary heating element is commingledwith the stream of heated material from the primary heating element andthe commingled streams are introduced to alternatereaction or cokingchambers maintained under a super atmospheric pressure of about 300pounds per square inch. A substantially equalized superatmosphericpressure of about 100 pounds per square inch is maintained in thefractionating, condensing and collecting portions of the system. Thisoperation may yield about 70% of premium motor fuel having an anti-knockvalue equivalent to a blend of about 75% iso-octane in normal heptane.The only other products ofthe process are about 100 pounds ofcarbonaceous material per barrel-of both primary and secondary chargingstock and about 400 cubic feet of .comprises about 25% uncondensablebarrel system.

As another typical example of an operation which. may be employed by theprocess of the present invention, the

material charged to the by weight of pulverized bituminous coal inadmixture with about 75% by weight of a 22 A. P. I. gravity fuel oil.The coal and oil mixture is subjected, in the primary heating element,to a temperature of about 870 F. under a super-atmospheriepressure ofabout 500 pounds per square inch. The secondary charging stock is a.Pennsylvania distillate of about 34 A. P. I. gravity which is subjected,together with reflux condensate froin the fractionator of the system, toa temperature in the secondaryheating element, of about 1000 F. under asuper-atmospheric pressure of approximately 100 pounds per square inch.The two streams of heated materials are commingled and introduced intoalternate coking chambers maintained under a super-atmospheric pressureof approximately 60 pounds per square inch which pressure issubstantially equalized in the fractionating, condensing and collectingportions of the system. This operation may yield approximately 50% ofmotor fuel having an octane number of about 72, the only other productsof the system being about 150 pounds of carbonaceous material per barrelof combined charging stock and about 300 cubic feet of uncondensable gasper barrel of material charged to the system.

It will be evident that the examples given are only illustrative of someof the many operations which may be practiced in accordance with theprinciples of the presentinvention and therefore donot limit theinvention in anysense.

By the term bituminous as used in the claims- I intend to include coal,lignite, peat, gilsonite, and similar materials.

I claim as my invention:

1. A process for the conversion of hydrocarbons into products of greatervalue, which comprises forcing a stream of solid bituminous materialsuch as coal and relatively heavy hydrocarbon charging oil through aheating zone where it is raised substantially in temperature to at least650 F., but without any substantial carbon. deposition, discharging theheated mixprimary charging stock ture into an enlarged reaction zonewhere separation takes place between'vapors and nonvaporous residue,subjecting the vapors to partial condensation-to condense the heavierfractions thereof, collecting the vapors remaining uncondensed afterpassage through the dephlegmating zone as the distillate product of theprocess, returning a stream of reflux condensate from said dephlegmatingzone and merging same with the stream of oil being passed through theheating zone, simultaneously forcing a second stream of hydrocarboncharging oil from a source outside the process and of lower boilingpoint than said heavy charging oil through a second independentlycontrolled zone and raising said latter stream to a temperature higherthan the temperature to which the stream passing through the firstheating zone is raised and discharging sa-idsecond heated stream intosaid enlarged reaction zone.

from the dephlegmating zone is admixed with the stream of oil beingforced through the second heating zone.

4. A process for the conversion of hydrocarbons into products of greatervalue, which comprises forcing a stream of solid bituminous materialsuchas coal and relatively heavy hydrocarbon charging oil through a heatingzone densed after passage through the dephlegmating zone as thedistillate product of the process, returning a stream of refluxcondensate from said dephlegmating zone and merging same with thestream-of oil being passed through the heating zone, simultaneouslyforcing a second stream of hydrocarbon charging oil from a sourceoutside the process and of lower boiling point than said heavy chargingoil through a second independently controlled zone and raising saidlatter stream to a temperature higher than the temperature to which thestream passing through the first heating zone is raised and dischargingsaid second heated stream into said enlarged reaction zone. I

5. A process which comprises passing a mixture of heavy charging oil and,lid bituminous material such as coal in a re tricted stream through aheating zone and h ating the same therein to at least 650 F. withoutsubstantial carbon deposition, simultaneously passing charging oil oflower boiling point than said heavy oil and from a source outside theprocess through a second heating zone maintained at higher temperaturethan the first-mentioned heating zone and heating the same to crackingtemperature therein, discharging the heated products from both saidheating zones into an enlarged distilling zone and commingling the sametherein whereby heat is transferred from the lighter oil to saidmixture, distilling the mixture substantially to coke in the distillingzone, and removing and condensing the vapors.

6. A process which comprises passing a mixture of heavy oil and solidbituminous material such as coal in a restricted stream through aheating zone and heating the same therein to at least 650 F. withoutsubstantial carbon deposition, simultaneously passing an oil of i -werboiling point than said heavyoil and containing gasoline hydrocarbons oflow anti-knock value through a second heating zone maintained at highertemperature than the first-mentioned heating zone and heating the sameto cracking temperature therein,-discharging the heated products fromboth said heating zones into an enlarged distilling zone and comminglingthe same therein whereby heat is transferred from the lighter oil tosaid mixture, distilling the mixture substantially to coke in thedistilling zone, dephlegmating the vapors to condense heavier fractionsthereof, supplying resultant reflux condensate to said second heatingzone, and finally condensing the dephlegmated vapors.

JACQUE C. MORRELL.

